T H E JOCRNAI, OF I N D U S T R I A L A X D ESGINEERING C H E X I S T R Y
1028
dry distillation of t h e wood was divided into two portions, t h e one, the major portion with a lithium salt insoluble in hot methyl alcohol; t h e other, small in amount, with a lithium salt soluble in methyl alcohol. The acids were liberated b y boiling with dilute sulfuric acid and extracting t h e cooled mixture with ether. Recrystallized from alcohol, the respective acids melted a t 78 and 8 ; " . T h e acid from the lithium salt insoluble in methyl alcohol, melting a t 7 8 ' , was further purified and t h e melting point rose t o 80-82'. This latter acid, presumably lignoceric acid, was compared with cerotic acid made from beeswax according t o t h e method employed. b y Marie.* T h e acid obtained from t h e wax melted a t 78-79'; .mixed with t h e acid from rotten wood melting a t So', t h e melting point of t h e mixture was 72-74'. T h e lowering of t h e melting point of t h e mixture shows t h a t the acid from t h e wood is not identical with cerotic acid. T h e wood acid mixed with lignoceric acid from peat soil gave a mixture melting at 79-81', so these acids are probably identical. Lignoceric acid forms a lead salt melting a t I I ~ ' , and a lithium salt decomposing about 190-195 0.3 The acid from t h e rotten wood gave a lead salt melting a t 116-II~', a lithium salt decomposing a t 195' and gradually liquefying t o 2 1 0 - 2 1 5 ' , a t which temperature it formed a brown liquid. From t h e solubility of t h e acid and its salts t h e percentage composition, t h e decomposing point of the lithium salt, t h e melting point of t h e lead salt, and t h e non-lowering of t h e melting point when mixed. with lignoceric acid from soil, i t may be concluded t h a t the acid derived from the rotten oak wood b y dry distillation is lignoceric acid identical with t h e lignoceric acid obtained b y Hell4 from beech wood t a r and from "carnaubon" from ox kidneys b y Rosenheim and MacLean.' The lignoceric acid, or a closely related substance, exists in t h e wood, for i t has been obtained b y extraction with alcohol. To obtain this acid t h e finely ground mood was extracted with hot alcohol and the part which separated on cooling was saponified with alcoholic soda. P a r t of t h e sodium salt was insoluble in hot alcohol. T h e filtrate from t h e hot alcoholic soda was freed f r o m alcohol, with replacement by water. T h e hot water mixture was filtered hot. The filtrate treated with sulfuric acid gave a crystalline acid which was purified b y crystallization from alcohol and ether. The free acid gave a lithium salt insoluble in methyl alcohol. The acid freed from lithium melted at 80-82' and was found t o be identical with t h e acid obtained from wood b y dry distillation. The second acid obtained in the dry distillation of wood, the acid melting a t 8 j ' with a lithium salt soluble in hot methyl alcohol, is believed t o be t h e inactive cerebronic acid described b y Levene and West.4 It is a white, easily pulverizable, non-hygroscopic substance soluble in ether and warm .alcohol. I 2
Ann. chim. p h y s . , ( 7 1 I (1896), 145. Hell and Hermann, Bev.. 13 (ISSO), 1713.
SOILFERTILITY INVES?IGATIONS DEPAR?MEK'C
OF A G R I C U L T U R E
WASHIKGTOB,
D. C.
METHOD OF EXTRACTION AS AFFECTING THE DETERMINATION OF PHOSPHORIC ACID IN SOILS By
HALEA N D a '. L. HARTLEP Received July 29, 1916
HaRRISON
While determining t h e phosphoric acid in soils during some work done in cooperation with t h e Missiouri State Fruit Experiment Station, occasion was also taken t o compare 0. L. Brauer's2 method of extracting t h e phosphoric acid 2 hrs. with 2 N HNOs with t h e official method of the Association of Official Agricultural Chemists3 of extracting I O hrs. with HC1 (SP. gr. I . 1 1 j). T h e soils were taken b y hIr. 4. D. Kilham of t h e
a Meyer, Brod, and Soyka, Mn?ialrh., 34 (1913), 1113.
1 2
Biochem. J . , 9 (1915), 103.
II
On cooling the alcohol it separates o u t in round masses, often in thick lamellae, which show a fine radiating structure. I t is free from nitrogen and burns with t h e smell of burning fat. I t s sodium salt is insoluble in water and not r e r y soluble in hot alcohol, especially in hot alkaline alcohol. On rubbing, i t becomes electrified. T h e general properties of t h e acid, its solubility, t h e solubility of t h e sodium and t h e lithium salts suggest t h e inactive form of cerebronic acid described b y Lerene and West. A further indication t h a t cerebronic acid exists in rotten wood is t h a t from a sodium alcoholate extract of t h e rotten wood material resembling cerebronic acid has been obtained. T h e alkaline alcohol solution was filtered hot and cooled in a n ice box. The precipitate which formed was slightly soluble in boiling water. The part insoluble in hot water was recrystallized successively from 95, 80 and 60 per cent alcohol. The nearly colorless material made a fine suspension in hot j o per cent alcohol and the turbid mixture passed through filter paper. ~On concentrating t h e solution, white matter settled out in mamillary masses, which on. drying melted a t 106-108O, t h e melting point of active cerebronic acid. This material was soluble in warm glacial acetic acid, from which i t settled out as a jelly on cooling. T h e p a r t most soluble in cold glacial acetic acid melted a t 90-94'. Cerebronic acid, as described b y Levene and Jacobs,' has three forms: ( I ) t h e optically active form melting a t 106-108'; ( 2 ) t h e inactive form melting a t 82-85'; and (3) a mixture of these melting about 92' All in all, it is believed t h a t cerebronic acid exists in rotten wood, though absolute proof was not obtained. A pleasing hypothesis is t h a t ccrebrosides exist on the living tree and t h a t from t h e cerebrosides there forms in t h e rottening of t h e wood, under t h e action of molds, bacteria, and t h e processes of oxidation, cerebronic acid and lignoceric acid. Of the presence of cerebrosides in wood no tests have been made; of t h e presence of cerebronic acid in rotten wood there are indications; and of t h e presence of lignoceric acid, a close relative of these, there is a satisfactory proof.
4 L O G . Lit. 6
Vol. 8 . S o .
8
J . Bid. Chem., 12 (1912), 381. THISJOURNAL, 6 (1914), 1004. Bureau of Chemistry, Bull. 101, 14.
Nov., 1916
T H E JOURNAL O F I N D U S T R I A L A N D ENGINEERING CHEMISTRY
Station from plots near Narionville, Mo., which were used for growing stra.wberries, and t o which fertilizer had been added as follows, per acre: SAMPLES 2h3 Check Plot ’
SAMPLES 6 & 15 375 Lbs. Bone Meal
SAMPLE13 SAMPLE16 300 Lbs. Sheep Manure 500 Lbs. 375 Lbs. Bone Meal No. 2 Manure
According t o Marrl t h e check plots show t h e following analysis: Volatile Matter ?... . 3.64 3 . . . . . 4.41
No.
.
Alumina 2.7; 2.10
Ferric Oxide 1.99 1.98
Magnesia 0.12 0.17
Potassium Insoluble TOTAL Lime Oxide Matter Per cent 0.55 0.10 90.78 99.40 0.43 0.11 90.80 100.00
At first a n effort was made t o precipitate t h e phosphoric acid with ammonium molybdate, dissolve t h e precipitate in ammonium hydroxide, reprecipitate with magnesia mixture, ignite and weigh as Mg2P207. However, owing t o t,he small amount of phosphoric acid present, accurate results could not be obtained. Thereafter, t h e determinations y e r e made volumetrically by adding a n excess of standard NaOH t o t h e phosphomolybdate precipitate and titrating t h e excess with standard HI SO^.^ Thefollowingresults show t h a t t h e 2-hr. digestion with z it’ H N 0 8 extracts as much phosphoric acid as t h e Io-hr. digestion with HC1 (sp. gr. I . 115). The Io-hr. diges1 2
Master’s Thesis, Drury College, 1915. Bureau of Chemistry, Bull. 107, 16.
1029
PER CENT PzOj FOUND IN SOILS Brauer’s Method: 2 hrs. Extraction with 2 N HNOa A . 0 A C. Method 10 hrs. Extraction with HC1 (sp. gr. 1.115) GRAVIMETRIC DETERMINATIONS VOLUMETRIC DETERMINATIONS Sample A. 0. A. C. A. 0. A. C. No. Brauer’s Method Method Brauer’s Method Method 2. . . . . . ....., ...... 0.052 0.048 0.050 0.054 3 . . . . .. 0,0532 0.0435 0.048 0.053 0.050 0,047 6. . , . , . ...... ...... 0.061 0,061 0.060 0.059 13. . . . . . 0.0511 0,0580 0.060 0.063 0.058 0.054 15 . . . . . . 0.0638 0.0638 0.0551 0.050 0.053 0.060 0.056 16. . . . . . 0.0700 0,0600 0.0435 0.062 0.064 0.056 0.061
tion with HC1 brings down considerable organic matter which it is very difficult t o remove completely with “0:. This organic matter produces a precipitate when the excess of acid is neutralized with ammonium hydrox.de in preparing t o add t h e ammonium molybdate, which requires considerable H S 0 3 t o redissolve, whereas t h e reaction with z N ” 0 3 brings down no interfxing substances. c 0 \‘CLUSIOSS I-The 2-hr. digestion with 2 N H N 0 8 extracts as much phosphoric acid as t h e Io-hr. digestion with HC1 (sp. gr. 1 , 1 1 5 ) . 11-The Io-hr. digestion with HC1 (sp. gr. I . 11j ) brings down very much more interfering substances than t h e 2-hr. digestion with z N HN08. WHITCOMB CHEXICAL LABORATORY DRURYCOLLEGE,SPRINGFIELD, MISSXRI
LABORATORY AND PLANT THE FLAME ARC IN CHEMICAL MANUFACTURE By W R. MOTTAND C. W. BEDFORD Received July 21, 1916
Photo-chemistry has developed into a n increasingly important science with a n extensive, scientific literature; however, but little progress has been reported on t h e use of light in t h e practical manufacture of chemicals-probably because of t h e lack of a powerful, eonstant light source. I n t h e search for such a light source, t o accelerate t h e chlorination of natural gas in t h e manufacture of chloroform, i t was found by one of t h e authors (C. W. B.) t h a t t h e high-amperage, white flame arc far excelled all other sources of light for this special work. As its advantages are so great, a discussion of its main features may be of interest and value t o others engaged in studying the effect of light on chemical reactions.
It is well established t h a t photo-chemical reaction is proportional t o t h e absorbed light energy.l Since chlorine is yellow (absorbing blue light) a n d bromine is red (absorbing blue and green light) so t h e maximum chemical power of light for these materials occurs in t h e short wave (blue, etc.) region of t h e spectrum. Chlorine a n d bromine are transparent in t h e far ultraviolet as shown by Mr. N. P. Peskov.2 For this reason, far ultraviolet light (i. e., beyond 3000 A . ) is unsatisfactory for causing chlorination and bromination. Among others, Baskerville a n d Riederer3 have shown t h a t t h e blue end of t h e visible spectrum is P. Lasareff, A n n . P h y s i k , 24 (1907), 661. “Quantitative Light-filter for the Ultraviolet Part of the Spectrum,” J . Russ. Phys. Chem. S O C47 , (1915), 918. 8 THISJOURNAL, 5 (19131, 5 1
2
more suitable t h a n ultraviolet light for t h e chlorination of methane. As was t o be expected, they found t h a t t h e presence of light of other wave lengths does not practically interfere with t h e action of t h e blue. and violet so t h a t light filters or sources of pure light are unnecessary. Our experience in t h e chlorination of methane hydrocarbons has led t o similar conclusions a n d a few experiments in t h e chlorination of aromatic hydrocarbons gave t h e same results.’ The snow-white flame arc, as will be shown below, is especially rich in blue light which is best for chlorination work. I n t h e reaction, hydrogen uniting with chlorine under light t o form hydrochloric acid (C12 Hz = zHCl), t h e more active region of t h e spectrum is from about 5160 A. t o 3700 A. according t o t h e experiments of Bunsen and Roscoe.2 The maximum action is exerted with t h e sola’r spectrum in t h e region of the Fraunhofer lines G (4308 A.) and H (3968 A.) according t o Fabre and Silberman.8 Draper says t h a t t h e maximum action in t h e indigo region’ is 700 times stronger t h a n in t h e extreme red.4 Bunsen a n d Roscoe found t h a t reaction power decreased gradually beyond line J . 6 Peskovc shows t h a t chlorine absorption ex-
+
1 I n the chlorination of methane, pure light is unnecessary because the products of the reaction are transparent to ordinary light to about 3000 A. The absorption spectrum of chloroform and carbon tetrachloride lies in the ultraviolet beyond about 3000 A. (See W. N. Hartley, 7th Int. Congwrs AppZ. Chem., 9 (1909), 88. The other product, hydrochloric acid, is still more transparent, being so to beyond 2500 A. (See E. J . Evans, Phil. Mag., 6 , No. 31 (Jan., 1916), 55.) * See Sheppard, “Photo-Chemistry,” page 118. 3 A n n . Chem. Phys., 131 37, 297. 4 See Eder’s “Handbuch der Photographie,” p. 323. 5 The E. I. du Pont de Nemours Powder Co., French Patent 453,406, Jan. 21, 1913, used in chlorinating hydrocarbons, glass tubes with daylight or the blue light of the quartz lamp 1 LOC. cit.
